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WO2022191634A1 - Réacteur à lit fluidisé et procédé de recyclage de précurseur de lithium faisant appel à celui-ci - Google Patents

Réacteur à lit fluidisé et procédé de recyclage de précurseur de lithium faisant appel à celui-ci Download PDF

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Publication number
WO2022191634A1
WO2022191634A1 PCT/KR2022/003358 KR2022003358W WO2022191634A1 WO 2022191634 A1 WO2022191634 A1 WO 2022191634A1 KR 2022003358 W KR2022003358 W KR 2022003358W WO 2022191634 A1 WO2022191634 A1 WO 2022191634A1
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Prior art keywords
active material
region
material powder
diameter
lithium
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English (en)
Korean (ko)
Inventor
성민지
차예리
손성열
김지민
서영빈
하현배
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SK Innovation Co Ltd
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SK Innovation Co Ltd
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Priority to CN202280014323.9A priority Critical patent/CN116829512A/zh
Priority to EP22767530.3A priority patent/EP4289793A4/fr
Priority to JP2023555674A priority patent/JP2024510990A/ja
Publication of WO2022191634A1 publication Critical patent/WO2022191634A1/fr
Priority to US18/464,894 priority patent/US20230420762A1/en
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1881—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving downwards while fluidised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00805—Details of the particulate material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00902—Nozzle-type feeding elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a fluidized bed reactor and a lithium precursor regeneration method using the same. More particularly, it relates to a fluidized bed reactor and a method for regenerating a lithium precursor from a waste lithium-containing compound using the same.
  • a secondary battery is a battery that can be repeatedly charged and discharged, and has been widely applied to portable electronic communication devices such as camcorders, mobile phones, and notebook PCs with the development of information communication and display industries.
  • Examples of the secondary battery include a lithium secondary battery, a nickel-cadmium battery, a nickel-hydrogen battery, and the like, and among them, the lithium secondary battery has high operating voltage and energy density per unit weight, and is advantageous for charging speed and weight reduction. It has been actively developed and applied in this respect.
  • a lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator (separator), and an electrolyte impregnating the electrode assembly.
  • the lithium secondary battery may further include, for example, a pouch-type casing accommodating the electrode assembly and the electrolyte.
  • a lithium metal oxide may be used as a positive active material of the lithium secondary battery.
  • the lithium metal oxide may additionally contain a transition metal such as nickel, cobalt, or manganese together.
  • the lithium metal oxide as the positive electrode active material may be prepared by reacting a lithium precursor and a nickel-cobalt-manganese (NCM) precursor containing nickel, cobalt, and manganese.
  • NCM nickel-cobalt-manganese
  • the positive electrode active material 20% or more of the manufacturing cost is required for manufacturing the positive electrode material.
  • environmental protection issues have recently been highlighted, research on recycling methods for positive electrode active materials is being conducted. In order to recycle the positive electrode active material, it is necessary to regenerate the lithium precursor from the spent positive electrode with high efficiency and high purity.
  • One object of the present invention is to provide a fluidized bed reactor for recovering a lithium precursor with high purity and high yield from a lithium-containing compound and a lithium precursor regeneration method using the same.
  • the lithium precursor regeneration method may include preparing a cathode active material powder including lithium composite oxide particles and having different particle sizes.
  • a preliminary precursor mixture is prepared by reducing the cathode active material powders in a fluidized bed reactor including a reactor body whose diameter is gradually or gradually reduced from top to bottom. And a lithium precursor is recovered from the preliminary precursor mixture.
  • the positive active material mixture includes a first active material powder, a second active material powder, and a third active material powder having different particle sizes
  • the reactor body is a first region in which the first active material powder is fluidized.
  • the first region, the second region, and the third region may be sequentially disposed from the upper portion of the reactor body.
  • a diameter of the first region may be greater than a diameter of the second region, and a diameter of the second region may be greater than a diameter of the third region.
  • the ratio of the diameter of the first region to the diameter of the third region may be 4 to 16.
  • a ratio of a diameter of the second region to a diameter of the third region may be 2 to 4.
  • the particle size of the first active material powder may be smaller than that of the second active material powder, and the particle size of the second active material powder may be smaller than that of the third active material powder.
  • the particle size of the first active material powder may be less than 10 ⁇ m
  • the particle size of the second active material powder may be 10 to 100 ⁇ m
  • the particle size of the third active material powder may be 100 ⁇ m or more.
  • the preparation of the preliminary precursor mixture may include injecting a reducing gas into the fluidized bed reactor.
  • the minimum flow rate in the first region of the reducing gas may be less than or equal to the terminal velocity of the first active material powder.
  • the maximum flow velocity in the second region of the reducing gas is greater than or equal to the minimum fluidization velocity of the second active material powder, and the maximum flow velocity in the third region of the reducing gas is the second 3 It may be greater than or equal to the minimum fluidization rate of the active material powder.
  • the reducing gas may be injected into the fluidized bed reactor at a flow rate of 8 to 18 cm/s.
  • a first connection portion connecting the first region and the second region, the diameter of which decreases from the first region to the second region, and the second region and the third region and a second connection part whose diameter decreases from the second area to the third area.
  • first connection part and the second connection part may further include a gas injection port located on a side surface.
  • the gas injection port may be disposed to be inclined on the side surface toward the upper side of the reactor body.
  • an angle between the side surfaces of the first and second connectors and the gas injection hole may be 45 to 90°.
  • a fluidized bed reactor for reducing a cathode active material includes a reactor body whose diameter is gradually or gradually reduced from top to bottom; an active material inlet into which a plurality of active material powders having different particle sizes and including lithium composite oxide particles are injected into the reactor body; and a gas inlet located at the lower portion of the reactor body and into which a reducing gas for fluidizing the active material powders is injected.
  • the fluidized bed reactor for reducing the cathode active material of the present application includes: a first connecting portion connecting the first region and the second region, and decreasing in diameter from the first region to the second region; and a second connecting portion connecting the second region and the third region, the diameter of which decreases from the second region to the third region.
  • first connection part and the second connection part may further include a gas injection port located on a side surface.
  • the present lithium precursor regeneration method can reduce active material powders having different particle sizes in a fluidized bed reactor including a reactor body whose diameter is gradually or gradually reduced from the top to the bottom. have. Accordingly, a high-yield, high-purity lithium precursor can be more easily obtained.
  • the temperature deviation according to the location in the reactor may be reduced. Accordingly, fluidization of the positive active material particles may be smoothly performed, and uniform mixing/reduction may be realized throughout the reactor.
  • the fluidized bed reactor may further include a gas injection port.
  • the gas injection port can prevent the problem of depositing the active material powder on the side of the fluidized bed reactor. Accordingly, the recovery efficiency of the lithium precursor may be further improved.
  • FIG. 1 is a schematic flowchart for explaining a lithium precursor regeneration method according to exemplary embodiments.
  • FIGS. 2 and 3 are schematic diagrams showing a fluidized bed reactor for reducing a cathode active material according to exemplary embodiments.
  • a lithium precursor is recovered from a positive electrode active material by using a fluidized bed reactor including a reactor body whose diameter is gradually or gradually reduced from top to bottom. Accordingly, the recovery efficiency of the lithium precursor may be further improved.
  • the term “precursor” is used to comprehensively refer to a compound including a specific metal to provide a specific metal included in the positive electrode active material.
  • FIG. 1 is a schematic flowchart for explaining a lithium precursor regeneration method according to exemplary embodiments.
  • cathode active material powders including lithium composite oxide particles and having different particle sizes may be prepared (eg, step S10 ).
  • the cathode active material powder may include lithium composite oxide particles obtained or regenerated from an electrical device or a chemical device.
  • the cathode active material powder may include various lithium composite oxide particles such as lithium oxide, lithium carbonate, and lithium hydroxide.
  • the cathode active material powder may include lithium composite oxide particles obtained or regenerated from a waste lithium secondary battery.
  • the waste lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
  • the positive electrode and the negative electrode may include a positive electrode active material layer and a negative electrode active material layer coated on the positive electrode current collector and the negative electrode current collector, respectively.
  • the positive active material included in the positive active material layer may include lithium composite oxide particles containing lithium and a transition metal.
  • the cathode active material may include lithium composite oxide particles represented by Formula 1 below.
  • M1, M2 and M3 are transition metals selected from Ni, Co, Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga or B can be In Formula 1, it may be 0 ⁇ x ⁇ 1.2, 2 ⁇ y ⁇ 2.2, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 0 ⁇ a+b+c ⁇ 1.
  • the positive active material may include NCM-based lithium composite oxide particles including nickel, cobalt, and manganese.
  • the NCM-based lithium composite oxide may be prepared by reacting a lithium precursor and an NCM precursor (eg, NCM oxide) with each other through a co-precipitation reaction.
  • embodiments of the present invention may be commonly applied to not only the cathode material including the NCM-based lithium composite oxide particles, but also to the lithium-containing lithium composite oxide cathode material.
  • the positive electrode may be separated and recovered from the waste lithium secondary battery.
  • the positive electrode includes a positive electrode current collector (eg, aluminum (Al)) and a positive electrode active material layer as described above, and the positive electrode active material layer may include a conductive material and a binder together with the above-described positive electrode active material. .
  • the conductive material may include, for example, a carbon-based material such as graphite, carbon black, graphene, and carbon nanotubes.
  • the binder is, for example, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile (polyacrylonitrile), polymethyl methacrylate (polymethylmethacrylate) may include a resin material.
  • PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • PVDF polyvinylidene fluoride
  • PVDF polyacrylonitrile
  • polymethyl methacrylate polymethylmethacrylate
  • the positive electrode active material powder may be prepared by separating the positive electrode from the waste lithium secondary lithium battery and grinding the separated positive electrode.
  • the crushing may be performed using a hammer mill, a shredder, a cut crusher, an impact crusher, or the like.
  • the positive active material powder may be prepared in a powder form by pulverization, and the positive active material powder may include particles having different particle sizes together.
  • the cathode active material powder may have a multimodal particle size distribution.
  • the multimodal particle size distribution may mean a case in which a plurality of main peaks in the distribution diagram are present in the particle size distribution diagram for particles.
  • the particle size of the positive electrode active material powder may be about 1 to 100 ⁇ m.
  • the cathode active material powder may include a first active material powder, a second active material powder, and a third active material powder having different particle sizes.
  • the particle size of the first active material powder may be smaller than that of the second active material powder, and the particle size of the second active material powder may be smaller than that of the third active material powder.
  • the particles having a particle size of less than about 10 ⁇ m included in the positive active material powder are the first active material powder, the particles having a particle size of about 10 to 100 ⁇ m are the second active material powder, and particles having a particle size of about 100 ⁇ m or more. may be defined as the third active material powder.
  • the positive electrode recovered before the pulverization may be heat-treated. Accordingly, desorption of the positive electrode current collector may be promoted during the pulverization treatment, and the binder and the conductive material may be at least partially removed.
  • the heat treatment temperature may be, for example, about 100 to 500 °C, preferably about 350 to 450 °C.
  • the positive electrode current collector may be removed by immersing the separated positive electrode in an organic solvent.
  • the positive electrode current collector may be removed from the separated positive electrode through centrifugation, and the positive electrode active material mixture may be selectively extracted by removing the positive electrode current collector.
  • the positive electrode current collector component such as aluminum is substantially completely separated and removed, and the positive electrode active material mixture in which the content of carbon-based components derived from the carbon-based conductive material and the binder is removed or reduced can be obtained.
  • a preliminary precursor mixture may be prepared from the cathode active material powder (eg, step S20 ).
  • a preliminary precursor mixture may be prepared by hydrogen reduction treatment of the cathode active material powder.
  • the hydrogen reduction treatment may be carried out in a fluidized bed reactor including a reactor body whose diameter is gradually or stepwise reduced from top to bottom.
  • the cathode active material powder may be introduced into the fluidized bed reactor and a reducing gas may be injected from a lower portion of the fluidized bed reactor.
  • the reducing gas may be hydrogen gas.
  • a cyclone may be formed from the lower portion of the fluidized bed reactor by the reducing gas and the preliminary precursor mixture may be generated while contacting the active material powder.
  • a carrier gas may be mixed with the reducing gas at the bottom of the fluidized bed reactor and injected. Accordingly, in the fluidized bed, gas-solid mixing can be promoted to promote a reaction, and a reaction layer of the preliminary precursor mixture in the fluidized bed reactor can be easily formed.
  • the carrier gas may include, for example, an inert gas such as nitrogen (N 2 ) or argon (Ar).
  • the preliminary precursor mixture may include a hydrogen reduction reaction product of a lithium-transition metal oxide included in the active material powder.
  • the preliminary precursor mixture may include a preliminary lithium precursor and a transition metal-containing reactant.
  • the preliminary lithium precursor may include lithium hydroxide, lithium oxide and/or lithium carbonate. According to exemplary embodiments, since the preliminary lithium precursor is obtained through a hydrogen reduction reaction, a mixed content of lithium carbonate may be reduced.
  • the transition metal-containing reactant may include Ni, Co, NiO, CoO, MnO, and the like.
  • the hydrogen reduction reaction may be performed at about 400 to 700 °C, preferably 450 to 550 °C.
  • a water washing treatment may be performed (eg, step S30 ).
  • the preliminary lithium precursor may be converted into a lithium precursor substantially composed of lithium hydroxide by the water washing treatment.
  • lithium oxide and lithium carbonate incorporated in the preliminary lithium precursor may be converted into lithium hydroxide by reacting with water, or may be removed by washing with water. Accordingly, a high-purity lithium precursor converted into a desired lithium hydroxide form can be produced.
  • the preliminary lithium precursor may be dissolved by reacting with water to substantially prepare an aqueous lithium hydroxide solution.
  • the transition metal-containing reactant included in the preliminary precursor mixture may be precipitated without dissolving or reacting in water by the washing treatment. Therefore, it is possible to separate the transition metal-containing reactant by filtration and obtain a lithium precursor including high-purity lithium hydroxide.
  • the water washing treatment may be performed under conditions in which carbon dioxide (CO 2 ) is excluded.
  • CO 2 carbon dioxide
  • the water washing treatment is performed in a CO 2 -free atmosphere (eg, an air atmosphere from which CO 2 is removed), regeneration of lithium carbonate can be prevented.
  • the water provided during the water washing treatment is purged using a CO 2 lacking gas (eg, nitrogen purging) to create a CO 2 -free atmosphere.
  • a CO 2 lacking gas eg, nitrogen purging
  • the precipitate-separated transition metal-containing reactant may be treated with an acid solution to form acid salt precursors of each transition metal.
  • sulfuric acid may be used as the acid solution.
  • the transition metal precursor NiSO 4 , MnSO 4 and CoSO 4 may be recovered, respectively.
  • lithium precursor substantially composed of lithium hydroxide by subjecting the preliminary precursor mixture produced by hydrogen reduction to water washing. Accordingly, it is possible to obtain a positive active material having a higher capacity and a longer life by preventing the by-product of other types of lithium precursors such as lithium carbonate.
  • the lithium precursor may include lithium hydroxide (LiOH), lithium oxide (Li 2 O), or lithium carbonate (Li 2 CO 3 ).
  • Lithium hydroxide may be advantageous as a lithium precursor in terms of charge/discharge characteristics, lifespan characteristics, high temperature stability, and the like of a lithium secondary battery. For example, in the case of lithium carbonate, it may cause a deposition reaction on the separator, thereby weakening lifespan stability.
  • FIGS. 2 and 3 are schematic diagrams showing a fluidized bed reactor for reducing a cathode active material according to exemplary embodiments.
  • the fluidized bed reactor 100 for reducing the cathode active material of the present application includes a reactor body 110 whose diameter is gradually or gradually reduced from top to bottom, and lithium composite oxide particles into the reactor body 110, It is located in the lower portion of the active material injection port 103 and the reactor body 110 into which a plurality of active material powders 50, 60, and 70 having different particle sizes are injected, and reduces the active material powders 50, 60, and 70 to fluidize. It may include a gas inlet 105 through which gas is injected.
  • the cathode active material powders 50 , 60 , and 70 have a first active material powder 50 , a second active material powder 60 , and a third active material powder 70 having different particle sizes. may include
  • a plurality of active material powders 50 , 60 , and 70 may be fluidized in the reactor body 110 , respectively.
  • the reactor body 110 may include a plurality of regions having different diameters in which the plurality of active material powders 50 , 60 , and 70 are fluidized, respectively.
  • the third active material powder 70 having a large particle size may be fluidized in the lower portion of the reactor body 110
  • the first active material powder 50 having a small particle size may be fluidized in the upper portion of the reactor body 110 .
  • the reactor body 110 includes a first region 111 in which the first active material powder 50 is fluidized, a second region 112 in which the second active material powder 60 is fluidized, and a third active material.
  • a third region 113 in which the powder 70 is fluidized may be included.
  • the active material powder having a small particle size is scattered and leaked, or the active material powder having a large particle size is not sufficiently fluidized. can do.
  • the temperature deviation according to the location in the reactor may be reduced. Accordingly, fluidization of the positive active material particles is smoothly performed, and uniform mixing of the particles can be realized throughout the reactor. Accordingly, excellent reaction efficiency can be realized even for a particle mixture having a different particle size distribution.
  • the diameter D1 of the first region 111 is greater than the diameter D2 of the second region 112
  • the diameter D2 of the second region 112 is the diameter of the third region 113 . It can be larger than (D3).
  • the particle size of the first active material powder 50 fluidized in the first region 111 is smaller than the particle size of the second active material powder 60 fluidized in the second region 112 , and the second region 112 .
  • the flow rate of the reducing gas injected into the fluidized bed reactor may be inversely proportional to the square of the diameter of each region. Therefore, the flow velocity of the reducing gas may be slower in the first region 111 than in the second region 112 , and slower in the second region 112 than in the third region 113 . Accordingly, the first active material powder 50 having a small particle size can be easily fluidized in the first region 111 , and the third active material powder 70 having a large particle size can be easily fluidized in the third region 113 . can
  • the diameter ratio D1 of the first region 111 to the diameter D3 of the third region 113 may be 5 to 10.
  • the diameter ratio D2 of the second region 112 to the diameter D3 of the third region 113 may be 2 to 4 .
  • fluidization of each of the first active material powder 50 , the second active material powder 60 , and the third active material powder 70 may be more easily performed. Accordingly, the recovery efficiency of the lithium precursor may be further improved.
  • the first region 111 , the second region 112 , and the third region 113 may be sequentially disposed from the top of the reactor body 110 .
  • the reducing gas may be injected in the upper direction from the lower portion of the reactor body 110 . Accordingly, the diameter of each region may decrease from the top to the bottom of the reactor body 110 .
  • the flow rate of the reducing gas injected into the bottom of the reactor body 110 may be decreased from the bottom to the top. Accordingly, in the first region 111 having a large diameter, the first active material powder 50 having a small particle size may be fluidized, and in the third region 113 having a small diameter, the third active material powder 70 having a large particle size may be fluidized. can be fluidized.
  • the gas inlet 105 is located in the lower portion of the reactor body 110, a reducing gas may be injected.
  • the reducing gas may include, for example, hydrogen gas.
  • the reducing gas may be injected into the lower portion of the reactor body 110 to fluidize and reduce the positive active material mixture included in the reactor body 110 .
  • the minimum fluidization speed to be described later may mean a minimum flow rate of the reducing gas for fluidizing the cathode active material powders 50 , 60 , and 70 .
  • the minimum fluidization rate may be calculated through Equation 1 below.
  • Equation 1 u mf is the minimum fluidization rate, ⁇ mf is the volume fraction of the active material powder particles, d p is the size of the active material powder particles, ⁇ g is the gas density of the reducing gas, ⁇ s is the solid density of the active material powder particles, ⁇ may be the gas viscosity of the reducing gas, ⁇ s may be the sphericity of the active material powder particles, and g may be the gravitational acceleration.
  • the flow rate of the reducing gas in the fluidized bed reactor 100 may be changed according to the diameter of the reactor body 110 included in the fluidized bed reactor (100).
  • the flow rate of the reducing gas may be reduced as the diameter of the reactor body 110 increases.
  • the minimum flow rate in the first region 111 of the reducing gas may be less than or equal to the terminal velocity of the first active material powder 50 .
  • the terminal velocity may mean a velocity in a state in which an object moves at a constant velocity when descending or moving in a fluid.
  • the terminal velocity may be calculated through Equation 2 below.
  • Equation 2 u t may be a terminal velocity, d p may be the size of the active material powder particles, and ⁇ s may be the sphericity of the active material powder particles.
  • the minimum flow rate in the first region 111 of the reducing gas is reduced to less than or equal to the terminal velocity of the first active material powder 50, the problem that the first active material powder 50 having a relatively small particle size is scattered effectively can be prevented.
  • the content of the fluidized first active material powder 50 may be further increased. Accordingly, the recovery efficiency of the lithium precursor may be further improved.
  • the maximum flow rate in the second region 112 of the reducing gas may be greater than or equal to the minimum fluidization velocity of the second active material powder 60, and the third region 113 of the reducing gas.
  • the maximum flow rate in the inside may be greater than or equal to the minimum fluidization speed of the third active material powder 70 .
  • the second active material powder 60 and the third active material powder 70 having large particle diameters may be more effectively fluidized. Accordingly, it is possible to effectively prevent the problem that the cathode active material powder is not fluidized and the lower portion of the fluidized bed reactor 100 is deposited.
  • the reducing gas may be injected into the fluidized bed reactor 100 at a flow rate of 8 to 18 cm/s or more.
  • the flow rate range when the flow rate range is satisfied, it is possible to prevent the first active material powder having a small particle size from scattering by the first region with a wide diameter positioned at the upper portion of the fluidized bed reactor, and at the same time, the particle size It is possible to effectively fluidize the large third active material powder. Accordingly, the recovery efficiency of the lithium precursor may be improved.
  • the fluidized bed reactor 100 for reducing the cathode active material of the present application connects the first region 111 and the second region 112 , and the second region 112 in the first region 111 .
  • Connecting the first connecting portion 121 and the second region 112 and the third region 113, the diameter of which decreases toward the It may include two connection parts 122 .
  • the first connection part 121 and the second connection part 122 prevent a sudden change in the diameter of the reactor body 110, thereby preventing the flow rate of the reducing gas in the reactor body 110 from rapidly decreasing. can Accordingly, it is possible to effectively prevent the active material powder from being deposited on the side surface of the reactor body 110 according to the decrease in the flow rate of the reducing gas.
  • the fluidized bed reactor for reducing the cathode active material of the present application may further include a gas injection hole 130 disposed on the side of the connection part 120 .
  • a gas injection hole 130 disposed on the side of the connection part 120 .
  • a reducing gas or the like may be injected into the gas injection port 130 .
  • the gas injected from the gas injection port 130 can effectively prevent the active material powder from being deposited on the side surface of the connection part 120 .
  • the gas injection port 130 may be disposed to be inclined on the side surface toward the upper side of the reactor body 110 . In this case, it is possible to more effectively prevent the problem that the positive electrode active material powder 50 , 60 , 70 is deposited on the side surface of the connection part 120 by the gas injection hole 130 disposed upward of the reactor body 110 .
  • the angle ⁇ between the side surface of the connection part 120 and the gas injection hole 130 may be 45 to 90°.
  • the angle ⁇ between the side surface of the connection part 120 and the gas injection hole 130 satisfies the above range, it is possible to more effectively prevent the problem that the active material powder is deposited on the side surface of the connection part 120 .

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  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
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Abstract

Un procédé de recyclage d'un précurseur de lithium selon la présente demande consiste à préparer une poudre de matériau actif de cathode comprenant des particules d'oxyde composite de lithium et ayant différentes tailles de particules. Un mélange précurseur préliminaire est préparé par réduction de la poudre de matériau actif de cathode dans un réacteur à lit fluidisé comprenant un corps de réacteur dont le diamètre diminue graduellement ou progressivement de haut en bas. Ensuite, un précurseur de lithium est récupéré à partir du mélange précurseur préliminaire.
PCT/KR2022/003358 2021-03-11 2022-03-10 Réacteur à lit fluidisé et procédé de recyclage de précurseur de lithium faisant appel à celui-ci Ceased WO2022191634A1 (fr)

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CN202280014323.9A CN116829512A (zh) 2021-03-11 2022-03-10 流化床反应器以及利用该流化床反应器的锂前驱体的再生方法
EP22767530.3A EP4289793A4 (fr) 2021-03-11 2022-03-10 Réacteur à lit fluidisé et procédé de recyclage de précurseur de lithium faisant appel à celui-ci
JP2023555674A JP2024510990A (ja) 2021-03-11 2022-03-10 流動層反応器及びそれを用いたリチウム前駆体の再生方法
US18/464,894 US20230420762A1 (en) 2021-03-11 2023-09-11 Fluidized bed reactor and method for recycling lithium precursor using same

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101555030A (zh) * 2009-05-04 2009-10-14 佛山市邦普镍钴技术有限公司 一种废旧锂离子电池阴极材料的回收与再生的方法
WO2016129732A1 (fr) * 2015-02-13 2016-08-18 주식회사 이엔드디 Procédé de régénération de déchets de précurseur de matériau actif d'électrode positive pour batterie rechargeable au lithium au moyen d'un broyeur à boulets
WO2017091562A1 (fr) * 2015-11-24 2017-06-01 Worcester Polytechnic Institute Procédé et appareil permettant de recycler des batteries au lithium-ion
KR102020238B1 (ko) * 2018-04-09 2019-09-10 에스케이이노베이션 주식회사 리튬 이차 전지의 활성 금속 회수 방법
KR20200052735A (ko) * 2018-11-07 2020-05-15 에스케이이노베이션 주식회사 리튬 전구체 재생 방법 및 리튬 전구체 재생 시스템

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4725309A (en) * 1986-03-17 1988-02-16 Hylsa, S.A. Method and apparatus for producing hot direct reduced iron
AT405521B (de) * 1996-05-17 1999-09-27 Voest Alpine Ind Anlagen Verfahren zum behandeln teilchenförmigen materials im wirbelschichtverfahren sowie gefäss und anlage zur durchführung des verfahrens
CN1181159C (zh) * 2001-03-16 2004-12-22 中国林业科学研究院林产化学工业研究所 生物质内循环锥形流化床气化工艺及设备
WO2003080874A1 (fr) * 2002-03-19 2003-10-02 Superior Graphite Co. Procede et appareil de reduction directe d'oxydes de fer dans un lit fluidise electrothermique et produit resultant
CN101117665A (zh) * 2006-08-03 2008-02-06 中国科学院过程工程研究所 氧化-还原焙烧高钙镁钛渣的流化床反应器
FI119379B (fi) * 2007-03-16 2008-10-31 Outotec Oyj Tapa tehostaa selkeytystä sekoitusreaktorissa ja sekoitusreaktori
KR101563338B1 (ko) 2013-06-27 2015-10-27 성일하이텍(주) 용매추출법을 이용한 리튬 함유 폐액으로부터 리튬의 회수방법
CN104801721B (zh) * 2015-05-15 2017-05-31 中国科学院过程工程研究所 一种制备纳米金属粉体的设备及方法
DE102015116476A1 (de) * 2015-09-29 2017-04-13 Outotec (Finland) Oy Verfahren und Anlage zur Herstellung von Uran oder einem Seltenen-Erden-Element
PL3571733T3 (pl) * 2017-01-23 2021-10-25 Basf Se Sposób wytwarzania materiałów katodowych i reaktor odpowiedni do przeprowadzenia wspomnianego sposobu
KR101998691B1 (ko) * 2018-10-04 2019-07-10 에스케이이노베이션 주식회사 리튬 전구체 재생 방법 및 리튬 전구체 재생 시스템

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101555030A (zh) * 2009-05-04 2009-10-14 佛山市邦普镍钴技术有限公司 一种废旧锂离子电池阴极材料的回收与再生的方法
WO2016129732A1 (fr) * 2015-02-13 2016-08-18 주식회사 이엔드디 Procédé de régénération de déchets de précurseur de matériau actif d'électrode positive pour batterie rechargeable au lithium au moyen d'un broyeur à boulets
WO2017091562A1 (fr) * 2015-11-24 2017-06-01 Worcester Polytechnic Institute Procédé et appareil permettant de recycler des batteries au lithium-ion
KR102020238B1 (ko) * 2018-04-09 2019-09-10 에스케이이노베이션 주식회사 리튬 이차 전지의 활성 금속 회수 방법
KR20200052735A (ko) * 2018-11-07 2020-05-15 에스케이이노베이션 주식회사 리튬 전구체 재생 방법 및 리튬 전구체 재생 시스템

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4289793A4 *

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EP4289793A4 (fr) 2025-01-22
JP2024510990A (ja) 2024-03-12

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